Process for selective hydrogenation of C--C double bonds in the presence of reducible, nitrogen-containing groups and new ruthenium complex compounds

ABSTRACT

Carbon-carbon double bonds are hydrogenated selectively in a compound containing a reducible, nitrogen-containing group if the hydrogenation is carried out in the presence of a ruthenium complex catalyst. Also disclosed are new ruthenium complexes for use in such selective hydrogenation.

This is a division of application Ser. No. 659,591, filed Oct. 11, 1984 and now U.S. Pat. No. 4,673,757.

The present invention relates to a new process for selective catalytic hydrogenation of C--C double bonds in compounds containing reducible, nitrogen-containing groups in the presence of ruthenium complex catalysts and new ruthenium complex compounds useful for such reduction.

It is known that C--C double bonds can be hydrogenated selectively, beside nitrogen-containing reducible groups, over solid catalysts. Palladium catalysts or platinum catalysts are used for this purpose. If the olefinic double bonds are not highly substituted, they can be hydrogenated, for example, without attack on a cyano group. Yields of up to 90% are thereby achieved (see Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), volume IV, 1c, Reduktion (Reduction) I (1980), page 168). However, the selectivity is frequently unsatisfactory. Thus, if platinum oxide is used for the hydrogenation of 1-cyanocyclohexene, only 31% of the desired cyanocyclohexane is obtained (see M. Freifelder, Practical Catalytic Hydrogenation, (1971), page 157).

The hydrogenation of unsaturated nitriles using rhodium complexes as homogeneous catalysts is attributed to G. Wilkinson. The hetero-functional cyano group is not hydrogenated on hydrogenation with the Wilkinson complex as the catalyst. However, deactivation of the catalyst may take place with nitriles, as a result of ligand exchange (see Houben-Weyl, loc. cit., pages 57 to 60).

Since rhodium complexes of the formula [(C₆ H₅)₃ P]₃ Rh^(I) X are also suitable for the hydrogenation of nitriles to amines (see German Auslegeschrift No. 1,793,616, column 2, line 51), it must be expected that their selectivity is not always adequate for the hydrogenation of olefinic double bonds adjacent nitrile groups.

Although it is known that halogen-containing ruthenium complexes chiefly hydrogenate terminal olefin bonds, selective hydrogenation, in particular of inner double bonds adjacent or near nitrogen-containing functional groups, has not hitherto been described. In contrast, it is known that ruthenium complexes already attack functional groups under hydrogenation conditions from 80° C. (see Houben-Weyl, loc. cit., page 56).

It is known from U.S. Pat. No. 3,454,644 that keto, formyl, nitrile and non-aromatic --C═C-- and --C.tbd.C-- groups can be hydrogenated with phosphine-containing ruthenium complexes of the type L_(n) MX₂ (L=CO or tertiary phosphine, n=3 or 4, M=ruthenium or osmium and X=halogen and/or hydrogen), all the groups of this type present always being hydrogenated.

Ruthenium complexes therefore cannot be expected to have a satisfactory selectivity for the hydrogenation of C--C double bonds, in particular non-terminal double bonds, adjacent reducible nitrogen-containing functional groups.

A process has now been found for selectively catalytically hydrogenating a carbon-carbon double bond in a compound possessing a reducible nitrogen-containing group, which comprises contacting said compound with hydrogen or a source of hydrogen in the presence of a catalytically active ruthenium complex which corresponds to the formula

    RuXL.sub.1 (L.sub.2).sub.2

in which

X represents chlorine, bromine, iodine or hydrogen,

L₁ represents an aromatic ligand of the formula ##STR1## in which R₁ to R₅ can be identical or different and represent hydrogen, methyl, ethyl or phenyl, it also being possible for in each case two adjacent radicals from the group R₁ to R₅ together to form a hydrocarbon radical such that L₁ overall represents a fused ring system, which optionally contains substituents which are inert under the reaction conditions, and

L₂ represents a ligand from the group comprising tertiary organophosphorus, organoarsene and organoantimony compounds, or

(L₂)₂ represents a bidentate bisphosphane ligand.

In formula (I), X preferably represents hydrogen or chorine.

Examples of L₁ ligands are cyclopentadienyl, pentamethylcyclopentadienyl, ethyltetramethylcyclopentadienyl, pentaphenylcyclopentadienyl and dimethyltriphenylcyclopentadienyl. Cyclopentadienyl is the preferred L₁ ligand.

Examples of L₂ ligands are those which correspond to the formulae ##STR2## in which R₆, R₇ and R₈ can be identical or different and denote alkyl, cycloalkyl, aryl or aralkyl radicals, it being possible for these radicals to be optionally substituted by alkyl, hydroxyl, alkoxy, carbalkoxy or halogen groups.

Examples of alkyl radicals here are straight-chain or branched, saturated hydrocarbon radicals with 1 to 20, preferably 1 to 12 and particularly prefeably 1 to 6, C atoms. Particularly preferred alkyl radicals are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.

Examples of cycloalkyl radicals here are cyclic, saturated hydrocarbon radicals with 5 to 12, preferably 5 to

7, C atoms, such as cyclopentyl, cyclohexyl and cycloheptyl.

Examples of aryl radicals here are aromatic hydrocarbon radicals from the benzene series with 6 to 18, preferably 6 to 12, C atoms, for example phenyl, biphenyl, naphthyl and anthracyl.

Examples of aralkyl radicals here are alkyl radicals which are substituted by aryl and which consist, in the aliphatic part, of a straight-chain or branched hydrocarbon radical with 1 to 6 C atoms and, in the aromatic part, of a radical of the benzene series, preferably phenyl. An example here is the benzyl radical.

The alkyl, cycloalkyl, aryl and aralkyl radicals described above can optionally be substituted by C₁ - to C₆ -alkyl, hydroxyl, C₁ - to C₆ -alkoxy, C₁ - to C₆ -carbalkoxy, fluorine or chlorine. Examples of alkyl substituents are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.

Examples of alkoxy substituents are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy and isohexoxy. Examples of carbalkoxy substituents are carbmethoxy; carbethoxy, carbisopropoxy and carbpropoxy. Of the substituents fluorine and chlorine, fluorine is preferred.

Preferred L₂ ligands are those of the formula (III). Examples of these are triphenylphosphane, diethylphenylphosphane, tritolylphosphane, trinaphthylphosphane, diphenylmethylphosphane, diphenylbutylphosphane, tris-(p-carbmethoxyphenyl)-phosphane, tris-(p-cyanophenyl)-phosphane, tributylphosphane, tris-(trimethylphenyl)-phosphanes, tris-(trimethoxyphenyl)-phosphanes, bis-(trimethylphenyl)-phenylphosphanes, bis-(trimethoxyphenyl)phenylphosphanes, trimethylphenyl-diphenylphosphanes, trimethoxyphenyldiphenylphosphanes, tris-(dimethylphenyl)-phenylphosphanes, tris-(dimethoxyphenyl)-phosphanes, bis-(dimethylphenyl)-phenylphosphanes, bis-(dimethoxyphenyl)-phenylphosphanes, dimethylphenyldiphenylphosphanes and dimethoxyphenyldiphenylphosphanes.

If the group (L₂)₂ in the formula (I) represents a bidentate bisphosphane ligand, this can correspond, for example, to the formula ##STR3## in which n represents an integer from 1 to 10 and the radicals R₉, R₁₀, R₁₁ and R₁₂ can be identical or different and correspond in meaning to the radicals R₆, R₇ and R₈ as described for formulae (III) to (VI).

Examples of bisphosphanes of this group are 1,2-bis-dianisylphosphanoethane and 1,4-bis-diphenylphosphanobutane.

Some of the ruthenium complexes of the formula

    RuXL.sub.1 (L.sub.2).sub.2                                 (I)

in which

L₁ denotes cyclopentadienyl,

L₂ denotes simple phosphanes or phosphites, such as triphenylphosphane, tritolylphosphane or trimethyl phosphite, and

X represents chlorine, bromine, iodine or hydrogen,

are known (see M. I. Bruce, N. J. Windsor, Aust. J. Chem. 30 (1977), pages 1601 to 1604).

The ruthenium complexes of the formula

    RuXL.sub.1 (L.sub.2).sub.2                                 (I)

in which

X is hydrogen,

can be obtained, for example, by hydrogenation of the corresponding ruthenium complexes of the formula (I) in which X is chlorine. This hydrogenation can be carried out, for example, by reaction with lithium alanate in ether (see T. Blackmore, M. I. Bruce and F. G. A. Stoue, J. Chem. Soc. Sect. A 1971, pages 2376 to 2382), or by reaction with sodium methylate in methanol (see T. Wilczewsky, M. Bochenska and J. F. Biernat, J. Organomet. Chem. 215 (1981), pages 87 to 96).

The ruthenium complexes of the formula

    RuXL.sub.1 (L.sub.2).sub.2                                 (I)

in which

X is chlorine,

can be obtained, for example, by reaction of hydrated ruthenium trichloride with an excess of the ligands L₁ and L₂ in ethanol (see M. I. Bruce and N. J. Windsor, Aust. J. Chem. 30 (1977), pages 1601 to 1604).

The ruthenium complexes of the formula

    RuXL.sub.1 (L.sub.2).sub.2                                 (I)

in which

X is bromine or iodine,

can be obtained, for example, simply by heating the corresponding ruthenium complexes of the formula (I) in which X is hydrogen with HBr or HI in methanol (see T. Wilczewsky, M. Bochenska, J. F. Biernat in J. Organomet. Chem. 215, pages 87 to 96).

For carrying out the process according to the invention, for example, 0.001 to 50 mmol of a catalytically active ruthenium complex of the type described above can be employed per mol of C--C double bond to be hydrogenated. Catalyst amounts of 0.01 to 10 mmol per mol of C--C double bond to be hydrogenated are preferably used. The process according to the invention is in general carried out in the temperature range from 20° to 250° C. Temperatures in the range from 80° to 150° C. are preferred.

The process according to the invention is in general carried out in the pressure range from 5 to 300 bar. Pressures below 5 bar are also possible, in which case, however, the reaction time usually has to be increased. The process according to the invention can likewise be carried out under high pressures than 300 bar, but this is associated with an increased technical effort. The process according to the invention is preferably carried out in the pressure range between 20 and 200 bar.

Compounds of the formulae (III), (IV), (V) and (VI) are preferably introduced into the process according to the invention only in the form of the ruthenium complexes of the formula (I) or (VII), that is to say not in the free form.

The process according to the invention is in general carried out in the liquid phase. The liquid reaction mixture can be a mixture of liquids which are present per se, that is to say a mixture of the starting materials and reaction products, or, in particular, if the starting materials and/or reaction products are solid under the reaction conditions, can consist of an added solvent, which is inert under the reaction conditions.

If the process according to the invention is to be carried out in the presence of a solvent, it is possible to add, for example, organic solvents which do not change under the reaction conditions. Possible examples of these are halogen-, alkyl- or alkoxy-substituted benzenes, such as chlorobenzene, toluene, xylenes and anisole; esters, such as ethyl acetate or dimethyl adipate; esters and ethers of polyols, such as glycol diacetate or tetraglyme; cyclic ethers, such as tetrahydrofuran and dioxane; lower alcohols, such as methanol and isopropanol; or ketones, such as acetone, butanone, diisopropyl ketone and cyclohexanone. Preferred solvents are toluene, isopropanol and butanone.

The solvents can be used in a weight ratio of, for example, 30:1 to 1:10, based on the starting substance. This ratio is preferably 15:1 to 1:3.

The most diverse compounds containing C--C double bonds and reducible nitrogen-containing groups can be selectively hydrogenated on the C--C double bonds by the process according to the invention. Examples of reducible nitrogen-containing groups which can be present are nitrile groups, and also oximine and/or imine groups. Several reducible nitrogen-containing groups, including different groups, may be present. The C--C double bonds can be olefinic double bonds, which can be in open-chain compounds in inner or terminal positions or in cyclic compounds. Examples of compounds which can be selectively hydrogenated in the manner according to the invention are alkene-nitriles, alkene-dinitriles, alkene-carbaldoximes, alkenecarbaldimines, in each case preferably containing 2 to 20 C atoms, and cycloalkene-nitriles, cycloalkene-carbaldoximes, cycloalkene-carbaldimines and nitroarylalkenes, in each case preferably containing 5 to 12 C atoms.

The starting material can furthermore optionally contain keto, carboxyl, carboxylic acid ester and/or carboxamide groups.

The yields and selectivities which can be achieved with the process according to the invention are very high. In general, the yields are between 90 and 100% and the selectivities are between 95 and 100%.

Since the process according to the invention is in general carried out under a hydrogen pressure, the course of the reaction can easily be observed by the drop in pressure. The end of the reaction can be recognised by a stationary pressure. The high selectivity is retained even if the reaction time is further increased. Examples of customary reaction times are 30 minutes to 10 hours; however, both shorter and longer reaction times may arise, depending on the catalyst, catalyst concentration and substrate.

The present invention furthermore relates to new ruthenium complex compounds of the formula

    RuZL.sub.3 (L.sub.4).sub.2                                 (VII)

in which

Z represents chlorine, bromine, iodine or hydrogen,

L₃ represents an optionally substituted cyclopentadienyl ligand and

L₄ represents a triorganophosphane ligand, with the proviso that L₃ only represents an unsubstituted cyclopentadienyl ligand if L₄ represents a triarylphosphane ligand containing at least one phenyl ring carrying at least one inert substituent which is not methyl, or

(L₄)₂ represents a bidentate bisphosphane ligand of the type Ph₂ P--(CH₂)_(n) --PPh₂, whereby n represents an integer from 1 to 10 and Ph represents an optionally substituted phenyl radical, with the proviso that L₃ only represents an unsubstituted cyclopentadienyl ligand if the biphosphane ligand is not (C₆ H₅)₂ P--(CH₂)₂ --P(C₆ H₅)₂.

The ligand L₄ can be, for example, a triorganophosphane ligand of the formula ##STR4## in which R₆, R₇ and R₈ can be identical or different and denote alkyl, cycloalkyl, aryl or aralkyl radicals, it being possible for these radicals optionally to carry inert substituents, such as alkyl, hydroxyl, alkoxy, carbalkoxy or halogen.

Examples of these are triphenylphosphane, diethylphenylphosphane, tritolylphosphane, trinaphthylphosphane, diphenylmethylphosphane, diphenylbutylphosphane, tris-(p-carbmethoxyphenyl)-phosphane, tris-(p-cyanophenyl)-phosphane, tributylphosphane, tris-(trimethylphenyl)-phosphanes, tris-(trimethoxyphenyl)-phosphanes, bis-(trimethylphenyl)-phenylphosphanes, bis-(trimethoxyphenyl)-phenylphosphanes, trimethylphenyl-diphenylphosphanes, trimethoxyphenyldiphenylphosphanes, tris-(dimethylphenyl)-phenylphosphanes, tris-(dimethoxyphenyl)-phosphanes, bis-(dimethylphenyl)-phenylphosphanes, bis-(dimethoxyphenyl)-phenylphosphanes, dimethylphenyldiphenylphosphanes and dimethoxyphenyldiphenylphosphanes.

The new ruthenium complex compounds of the formula

    RuZL.sub.3 (L.sub.4).sub.2                                 (VII)

can be obtained, for example, by reacting hydrated ruthenium trichloride with an excess of the ligands L₃ and L₄ in ethanol, or by reacting RuClL₃ (PPh₃)₂ with an excess of a ligand L₄ in ethanol.

To avoid long reaction times, it can be advantageous to run these reactions at elevated reaction temperatures in the presence of solvents, such as higher alcohols, for example butanol or hexanol.

The new ruthenium complexes according to the invention are in general obtained in yields of up to 90%, and in some cases even more.

It was not to be expected that the new ruthenium complexes of the formula (VII) in which sterically hindered ligands are present can be prepared in a similarly simple manner to ruthenium complexes with simple ligands.

The use of the new ruthenium complex compounds of the formula

    RuZL.sub.3 (L.sub.4).sub.2                                 (VII)

for selective hydrogenation of C--C double bonds has likewise already been described above.

The following examples illustrate the present invention, without in any way limiting it.

EXAMPLES Examples 1 to 9

A 15% strength solution of the educt in butanone and 0.03 mol % of the catalyst were initially introduced into a stirred stainless steel autoclave with a capacity of 0.3 liter, the autoclave was closed and the mixture was heated to the given temperature, under a hydrogen pressure. The pressure was kept at the given value by regular subsequent forcing in of hydrogen. As soon as no further drop in pressure occurred, the mixture was cooled and let down. The reaction solution was investigated by gas chromatography and worked up by distillation, the product isolated being investigated by spectroscopy (IR and NMR) for any hydrogenated nitrogen-containing groups present.

The starting materials, reaction conditions and results were as follows, Cp representing cyclopentadienyl, Ph representing phenyl, MeO representing methoxy and Me representing methyl, and selectivity meaning the yield of the stated product, based on the conversion.

Example 1

Educt: cyclohex-3-ene-nitrile, product: cyclohexanenitrile, catalyst: RuCl(Cp)(PPh₃)₂, reaction temperature: 120° C., reaction pressure: 130 bar, conversion: 100%, selectivity: 100%.

Example 2

Educt: cyclohex-3-ene-nitrile, product: cyclohexanenitrile, catalyst: RuH(Cp)(PPh₃)₂, reaction temperature: 120° C., reaction pressure: 140 bar, conversion: 100%, selectivity: 100%.

Example 3

Educt: cyclohex-3-ene-carbaldoxime, product: cyclohexanecarbaldoxime, catalyst: RuCl(Cp)(PPh₃)₂, reaction temperature: 120° C., reaction pressure: 140 bar, conversion: 90%, selectivity: 100%.

Example 4

Educt: cyclohex-3-ene-nitrile, product: cyclohexanenitrile, catalyst: RuCl(1,2,4-Ph₃ C₅ Me₂)(PPh₃)₂, reaction temperature: 120° C., reaction pressure: 120 bar, converson: 100%, selectivity: 100%.

Example 5

Educt: acrylonitrile, product: propionitrile, catalyst: RuH(Cp)[(4-MeO--C₆ H₄)₃ P]₂, reaction temperature: 120° C., reaction pressure: 130 bar, conversion:100%, selectivity: 100%.

Example 6

Educt: cyclohex-3-ene-N-phenylcarbaldimine, product: cyclohexane-N-phenylcarbaldimine, catalyst: RuCl(Cp)(PPh₃)₂, reaction temperature: 120° C., reaction pressure: 130 bar, conversion: 90%, selectivity: 98%.

Example 7

Educt: cyclohex-3-ene-nitrile, product: cyclohexanenitrile, catalyst RuCl(Cp)(PPh₃)₂, reaction temperature: 170° C., reaction pressure: 150 bar, conversion: 100%, selectivity: 100%.

Example 8

Educt: cyclohex-3-ene-nitrile, product: cyclohexanenitrile, catalyst: RuCl(Cp)[(2-Me--C₆ H₄)₃ P]₂, reaction temperature: 120° C., reaction pressure: 130 bar, conversion: 100%, selectivity: 100%.

Example 9

Educt: cyclohex-3-ene-nitrile, product: cyclohexanenitrile, catalyst: RuCl(Cp)[(2,4,6-Me₂ C₆ H₂)₃ P]₂, reaction temperature: 120° C., reaction pressure: 120 bar, conversion: 100%, selectivity: 100%.

Examples 10 to 18

All the experiments were carried out under a protective gas atmosphere (argon or nitrogen).

Example 10 Preparation of RuCl(Me₅ C₅)(PPh₃)₂

4.0 g of triphenylphosphane were dissolved in 100 ml of boiling ethanol in a glass flask, and 1.0 g of RuCl₃.3H₂ O, dissolved in 30 ml of ethanol, and 5.0 g of pentamethylcyclopentadiene, dissolved in 20 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 6 hours and allowed to cool slowly (0° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 1.2 g, melting point: 152°-154° C.

IR (cm⁻¹): 3060, 1590, 1570, 1480, 1435, 1190, 1120, 1090, 740, 695 and 520.

Example 11 Preparation of RuCl(Cp)[(4-MeO--C₆ H₄)₃ P]₂

5.4 g of (4-MeOC₆ H₄)₃ P were dissolved in boiling ethanol in a glass flask and 1.0 g of RuCl₃.3H₂ O, dissolved in 30 ml of ethanol, and 8.0 g of cyclopentadiene, dissolved in 20 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 4 hours and allowed to cool slowly (5° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 1.0 g, melting point: 190° C.

IR (cm⁻¹): 3040, 1595, 1570, 1500, 1290, 1260, 1180, 1120, 1025, 830, 800 and 540.

Example 12 Preparation of RuCl(Cp)(Ph₂ PC₂ H₅)₂

3.5 g of Ph₂ PC₂ H₅ were dissolved in 100 ml of boiling ethanol in a glass flask and 1.0 g of RuCl.3H₂ O, dissolved in 30 ml of ethanol, and 8.0 g of cyclopentadiene, dissolved in 20 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 1 hour and allowed to cool slowly (0° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 1.5 g, melting point: 182°-188° C.

IR (cm⁻¹): 3050, 1590, 1570, 1480, 1435, 1085, 1000, 935, 910, 850, 840, 695, 530, 520 and 500.

Example 13 Preparation of RuCl(Cp)[Ph₂ P(CH₂)₄ PPh₂

4.8 g of Ph₂ P(CH₂)₄ PPh₂ were dissolved in 100 ml of boiling ethanol in a glass flask and 1 g of RuCl₃.3H₂ O, dissolved in 30 ml of ethanol, and 8.0 g of cyclopentadiene, dissolved in 20 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 2 hours and allowed to cool slowly (5° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 0.4 g, melting point: >220° C.

IR (cm⁻¹): 3060, 1590, 1570, 1480, 1435, 1120, 1090, 1000, 880, 745, 725, 695, 540 and 520.

Example 14 Preparation of RuCl(Cp)[(2,4,6-Me₃ C₆ H₂)₃ P]₂

7.1 g of (2,4,6-Me₃ C₆ H₂)₃ P were dissolved in 100 ml of boiling ethanol in a glass flask and 1.0 g of RuCl₃.3H₂ O, dissolved in 30 ml of ethanol, and 8.0 g of cyclopentadiene, dissolved in 20 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 6 hours and allowed to cool slowly (0° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 0.7 g, melting point: >230° C.

IR (cm⁻¹): 3080, 1700, 1585, 1520, 1430, 1410, 1325, 1290, 1170, 1140, 1100, 1065, 1020, 865, 810, 780, 705 and 540.

Example 15 Preparation of RuCl(Ph₅ C₅)(PPh₃)₂

4.0 g of triphenylphosphane were dissolved in 100 ml of boiling ethanol in a glass flask and 1.0 g of RuCl₃.3H₂ O, dissolved in 30 ml of ethanol, and 5.0 g of pentaphenylcyclopentadiene, dissolved in 30 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 4 hours and allowed to cool slowly (5° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 2.8 g, melting point: 230° C. (decomposition).

IR (cm⁻¹): 3060, 1590, 1570, 1480, 1430, 1190, 1090, 1000, 745, 695, 550 and 520.

Example 16 Preparation of RuCl(2,4-dimethyltriphenylcyclopentadienyl)(PPh₃)₂

4.0 g of triphenylphosphane were dissolved in 100 ml of boiling ethanol in a glass flask and 1.0 g of RuCl₃.3H₂ O dissolved in 30 ml of ethanol, and 2.3 g of 2,4-dimethyltriphenylcyclopentadiene, dissolved in 30 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 4 hours and allowed to cool slowly (5° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 2.8 g, melting point: 196°-198° C.

IR (cm⁻¹): 3060, 1590, 1570, 1480, 1435, 1190, 1090, 1000, 740, 695, 540 and 520.

Example 17 Preparation of RuCl(Cp)[(4-Me₂ NC₆ H₄)₃ P]₂

6.0 g of (Me₂ NC₆ H₄)₃ P were dissolved in 100 ml of boiling ethanol in a glass flask and 1.0 g of RuCl₃.3H₂ O, dissolved in 30 ml of ethanol, and 6 g of cyclopentadiene, dissolved in 20 ml of ethanol, were rapidly added in succession. The mixture was boiled under reflux for a further 4 hours and allowed to cool slowly (5° C.) and the crystals precipitated were filtered off with suction. These were washed with water, ethanol, ether and hexane and dried in vacuo.

Yield: 1.1 g, melting point: >230° C.

IR (cm⁻¹): 3040, 2890, 2810, 1600, 1550, 1520, 1450, 1340, 1290, 1230, 1205, 1165, 1120, 945, 820, 650, 630, 540 and 505.

Example 18 Preparation of RuH(Cp)[(4-MeOC₆ H₄)₃ P]₂

0.3 g of sodium was dissolved in 100 ml of methanol, 1 g of RuCl(Cp)[(4-MeOC₆ H₄)₃ P]₂ was added and the suspension formed was stirred at room temperature for 1 hour. The mixture was stirred at 50° C. for a further 30 minutes and cooled with ice and the crystals were filtered off with suction and washed with ether and hexane.

Yield: 0.9 g, melting point: >230° C.

IR (cm⁻¹): 3060, 1935, 1580, 1480, 1280, 1240, 1160, 1100, 1010, 810 and 780. 

What is claimed is:
 1. A ruthenium complex compound of the formula

    RuZL.sub.3 (L.sub.4).sub.2

in which Z represents chlorine, bromine, iodine or hydrogen, L₃ represents a cyclopentadienyl, pentamethylcyclopentadienyl, ethyltetramethylcyclopentadienyl, pentaphenylcyclopentadienyl or dimethyltriphenylcyclopentadienyl and L₄ represents a triorganophosphane ligand of the formula ##STR5## in which R₆, R₇ and R₈ can be identical or different and denote alkyl, cycloalkyl, aryl or aralkyl radicals, or alkyl, cycloalkyl, aryl or aralkyl substituted by alkyl, hydroxyl, alkoxy, carbalkoxy, or halogen, with the proviso that L₃ only represents an unsubstituted cyclopentadienyl ligand if L₄ represents a triarylphosphane ligand containing at least one phenyl ring carrying at least one inert substituent selected from alkyl, hydroxyl, alkoxy, carbalkoxy and halogen which is not methyl, or (L₄)₂ represents a bidentate bisphosphane ligand of the type Ph₂ P--(CH₂)_(n) --PPh₂, whereby n represents an integer from 1 to 10 and Ph represents phenyl or phenyl substituted by alkyl, hydroxyl, alkoxy, carbalkoxy or halogen, with the proviso that L₃ only represents an unsubstituted cyclopentadienyl ligand if the bisphosphane ligand is not (C₆ H₅)₂ --P--(CH₂)₂ --P(C₆ H₅)₂.
 2. A ruthenium complex according to claim 1 wherein L₄ triorganophosphane ligand, with the proviso that L₃ only represents an unsubstituted cyclopentadienyl ligand if L₄ represents a triarylphosphane ligand containing at least one phenyl ring carrying at least one inert substituent which is not methyl.
 3. A ruthenium complex compound according to claim 1 wherein (L₄)₂ represents a bidentate bisphosphane ligand of the type Ph₂ P--(CH₂)_(n) --PPh₂, whereby n represents an integer from 1 to 10 and Ph represents phenyl or phenyl substituted by alkyl, hydroxyl, hydroxyl, alkoxy, carbalkoxy or halogen, with the proviso that L₃ only represents an unsubstituted cyclopentadienyl ligand if the bisphosphane ligand is not (C₆ H₅)₂ P--(CH₂)₂ --P(C₆ H₅)₂.
 4. A ruthenium complex compound according to claim 1 of the formula

    RuCl(Cp)[(4-MeOC.sub.6 H.sub.4).sub.3 P].sub.2

wherein Me represents methyl; Cp represents cyclopentadienyl.
 5. A ruthenium complex compound according to claim 1 of the formula

    RuCl(Cp)[Ph.sub.2 P(CH.sub.2).sub.4 PPh.sub.2 ]

wherein Cp represents cyclopentadienyl and Ph represents phenyl.
 6. A ruthenium complex compound according to claim 1 which isRuCl(2,4-dimethyltriphenylcyclopentadienyl)(PPh₃)₂.
 7. A ruthenium complex compound according to claim 1 which is

    RuCl(Cp)[Ph.sub.2 P--(CH.sub.2).sub.3 --PPh.sub.2 ]

wherein Cp represents cyclopentadienyl and Ph represents phenyl.
 8. A ruthenium complex compound according to claim 1 which is

    RuH(Cp)[(4-MeOC.sub.6 H.sub.4).sub.3 P].sub.2

wherein Cp represents cyclopentadienyl and Me represents methyl. 